EP0152086B1 - Matériau d'enregistrement électrophotographique - Google Patents

Matériau d'enregistrement électrophotographique Download PDF

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Publication number
EP0152086B1
EP0152086B1 EP85101403A EP85101403A EP0152086B1 EP 0152086 B1 EP0152086 B1 EP 0152086B1 EP 85101403 A EP85101403 A EP 85101403A EP 85101403 A EP85101403 A EP 85101403A EP 0152086 B1 EP0152086 B1 EP 0152086B1
Authority
EP
European Patent Office
Prior art keywords
recording material
photoconductor
dyes
sensitizing dye
zinc oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP85101403A
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German (de)
English (en)
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EP0152086A1 (fr
Inventor
Werner Dr. Dipl.-Chem. Franke
Richard Brahm
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0152086A1 publication Critical patent/EP0152086A1/fr
Application granted granted Critical
Publication of EP0152086B1 publication Critical patent/EP0152086B1/fr
Expired legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0664—Dyes
    • G03G5/0666—Dyes containing a methine or polymethine group
    • G03G5/0668—Dyes containing a methine or polymethine group containing only one methine or polymethine group
    • G03G5/067—Dyes containing a methine or polymethine group containing only one methine or polymethine group containing hetero rings
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/09—Sensitisors or activators, e.g. dyestuffs

Definitions

  • the present invention relates to an electrophotographic recording material, consisting of an electrically conductive support and a photoconductive layer containing photoconductor, sensitizing dye, binder and conventional additives.
  • layers for electrophotographic reproduction which contain zinc oxide as the photoconductor and whose spectral sensitivity is in the range of the boring UV light around 350 nm to around 400 nm.
  • these layers are provided with dyes of different classes of compounds. These include triphenylmethane dyes, diarylmethane dyes, monomethine cyanines, trimethine cyanines, styryl dyes, oxonols, merocyanines, complex cyanines, azenium dyes, azo dyes, anthraquinone dyes, indigo dyes, vinylene dyes, azomethines (GB-PS 1 020 052 540).
  • sensitizations which can also be achieved in zinc oxide photoconductor layers often have the disadvantage that they have a very broad base of spectral sensitization, which is particularly the case, for example, for eosin, bromophenol blue or rhodamine in connection with a disadvantageous residual coloration of the photoconductive layer or of the carrier material, such as Paper that appears.
  • the recording material proves to be less dark chamber safe.
  • Another disadvantage is that the maximum sensitization is sometimes not sharp. The maximum is often also not in the area in which the light source used for exposure emits most, which is of crucial importance, for example, in the case of a recording material for laser beam exposure.
  • the spectral sensitivity to light is often increased, but the general sensitivity is reduced or not improved.
  • the dyes used often strongly stain the photoconductive layer, which is a hindrance for some areas of application, for example copy and registration papers.
  • the sensitizing dyes used according to the invention are distinguished by an intensive and narrow sensitizing spectrum with a sharp maximum at approximately 495 nm and a pronounced steep drop towards the longer-wave spectral range. This ensures a high level of dark-chamber security against longer-wave light already from approx. 530 nm. This provides additional security and better quality of the manufactured products through visual control of the work processes and more pleasant working conditions.
  • the recording material is therefore outstandingly suitable for argon ion lasers which emit at 488 nm (514 nm) and for light sources emitting in the similar range.
  • the attached figure represents a sensitization spectrogram for a zinc oxide photoconductor layer sensitized according to the invention, which was obtained by exposure to a high pressure xenon lamp XBO 150/1 through an interference filter Veril R-60, No. B 71542.14 with gray wedge and toner development. The steep drop after the longer-wave part of the spectrum and the pronounced selective maximum are clearly indicated.
  • the recording material according to the invention is suitable, for example, as oscillograph paper or for printing plates which are used in machines which are used for the production of web offset printing formes (for example Laserite R RE from Hoechst AG). It is also suitable for use as a second copy in the laser exposure of printing plates.
  • the high sensitivity of the recording material is particularly advantageous compared to organic photoconductor layers, caused by the inherently higher basic sensitivity of these inorganic photoconductor layers in conjunction with the intensive spectral sensitization.
  • the sensitizing dyes according to the invention can be prepared as described in DE-PS 704141 or US : PS 2 503 776.
  • the concentration of the sensitizing dyes according to the invention depends on the photoconductor layer used in the individual case, the desired effect and also on the sensitizing dyes used.
  • An addition in the range of about 0.01 to 5 percent by weight is customary, preferably about 0.05 to 0.5 percent by weight, based on the weight of the photoconductor present, is used.
  • the recording material in which charge generation and charge transport can take place in one or more layers, contains ZnO-based photoconductors.
  • the grain size of the photoconductive zinc oxide is, for example, 0.1 to 15 micrometers.
  • the photoconductor containing a suitable insulating binder or a binder mixture This layer preferably has a specific resistance which is approximately between 10 7 and 10 14 ⁇ -cm.
  • the photoconductive layer can contain between 50 and 97 percent by weight of the photoconductive particles, based on the binder.
  • a preferred weight ratio of the binder to the particles is between 1: 4 and 1:10.
  • Any polymeric or resinous binder or a mixture of polymeric binders known for use in electrophotographic layers containing zinc oxide photoconductive can be used.
  • Suitable binders have a resistance which is higher than the inherent resistance of the photoconductive zinc oxide particles.
  • Suitable are, for example, electrically insulating, organic, resinous binders of the polyurethane, polyester, polycarbonate, polystyrene, chlorinated rubber, acrylic, alkyd, silicone, or vinyl acetate copolymer type, for example vinyl chloride acetate resin.
  • the photoconductive layers can be applied from an organic solvent or a solvent mixture, from an emulsion of organic solvents and water or from an aqueous medium.
  • the layers of the recording material can be flat or cylindrical and in a known manner from a metal plate, a metal foil, from metallized papers or metallized foils, from electrically conductive papers or from papers or foils that are coated with an electrically conductive plastic, or in another Documents made conductive.
  • Toner images can be produced on the recording material according to the invention in a known manner. However, it is also possible to transfer either the charge image or the toner image to an image-receiving material.
  • the electrophotographic recording material can contain leveling agents and plasticizers and / or adhesion promoters as conventional additives in the photoconductive layer and / or between the support and the photoconductive layer.
  • a highly wet-strength backing paper with a basis weight of about 100 g / m 2 which had been provided on the back with a binder layer containing carbon black particles for the purpose of electrical conductivity, was equipped on the front with a barrier layer against organic solvents and calendered.
  • the image-receiving layer was prepared as follows: 100 parts by weight of photoconductive zinc oxide were mixed together with 40 parts by weight of a 50% solution of a modified multipolymer of the vinyl acetate in toluene. The mixture was ball-milled for about 3 hours and then applied to the paper layer support by means of a wire doctor knife to a dry layer weight of 25 to 30 g / m 2 . 50 mg of the sensitizing dye according to Formula 2 from the formula table had been added to the solution.
  • the layer was charged and imaged with a corona (voltage 5 kV negative) at a distance of 25 mm.
  • the material was without disturbing residual color and showed a pronounced selective sensitization with a maximum of 500 nm and a steep drop towards the long-wave part of the spectrum.
  • a coating solution as described in Example 1 was applied to a 100 f.Lm thick aluminum foil. After the solvent had evaporated, an approximately 5 ⁇ m thick photoconductive layer resulted.
  • the layer was charged by means of corona and imaged with an argon ion laser in the power range 0.2 to 0.5 mW (nominal power 50 mW, output power 15 mW) at a feed of 400 lines / cm in a conventional automatic machine which is used to produce printing forms and further processed in the manner customary for zinc oxide printing plates.
  • an argon ion laser in the power range 0.2 to 0.5 mW (nominal power 50 mW, output power 15 mW) at a feed of 400 lines / cm in a conventional automatic machine which is used to produce printing forms and further processed in the manner customary for zinc oxide printing plates.
  • the printing plate was selective with a maximum at 500 nm and sensitive with steep drop to the long-wave region of the spectrum, as is shown in the figure, and is characterized by high dark chamber security.
  • a recording material was produced which, instead of the sensitizing dye according to the invention, contained the cyanine dye Astrazonorange R (C.I. 48040), according to DE-PS 2 526 720.
  • the sensitizer was ineffective. The material could not be illustrated.
  • the paper base was, as described in Example 1, provided with a layer containing zinc oxide, which contained a copolymer of vinyl acetate and maleic acid as a binder and, as described in Example 1, was sensitized.
  • the paper was practically free of residual staining, while comparison papers, which had been sensitized with a mixture of bromophenol blue (50 mg), fluorescein (50 mg), Rose Bengale (270 mg), eosin (400 mg), based on 100 g of zinc oxide, were strong showed red residual color.
  • the recording material according to the invention could be processed in the red light and also in yellow light without damage to the image, while with the same treatment the comparison material showed a disappearance or a significant weakening of the image or the registered curve.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Photoreceptors In Electrophotography (AREA)

Claims (3)

1. Matériau de reproduction électrophotographique, comprenant un support conducteur de l'électricité et une couche photoconductrice, contenant un photoconducteur, un colorant sensibilisateur, un liant et des additifs habituels, caractérisé par la combinaison d'oxyde de zinc en tant que photoconducteur et d'un composé de formule générale :
Figure imgb0010
dans laquelle
R représente le chlore ou le brome,
R1 est un alkyle de 1 à 3 atomes de carbone,
R2 est ―(CH2)n―SO3H ou ―(CH2)2―COOH,
R3 est ―(CH2)n―SO3 - ou ―(CH2)2―COO- et
m est 1 ou 2 et
n est 3 ou 4

en tant que colorant sensibilisateur dans la couche photoconductrice.
2. Matériau de reproduction selon la revendication 1, caractérisé en ce que le colorant sensibilisateur est un composé de formule suivante :
Figure imgb0011
3. Matériau de reproduction selon les revendications 1 ou 2, caractérisé en ce que le colorant sensibilisateur est présent en des quantités allant de 0,05 à 0,5 % en poids, par rapport au photoconducteur utilisé.
EP85101403A 1984-02-16 1985-02-09 Matériau d'enregistrement électrophotographique Expired EP0152086B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3405487 1984-02-16
DE19843405487 DE3405487A1 (de) 1984-02-16 1984-02-16 Elektrophotographisches aufzeichnungsmaterial

Publications (2)

Publication Number Publication Date
EP0152086A1 EP0152086A1 (fr) 1985-08-21
EP0152086B1 true EP0152086B1 (fr) 1987-11-11

Family

ID=6227862

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85101403A Expired EP0152086B1 (fr) 1984-02-16 1985-02-09 Matériau d'enregistrement électrophotographique

Country Status (4)

Country Link
US (1) US4663261A (fr)
EP (1) EP0152086B1 (fr)
JP (1) JPS60192956A (fr)
DE (2) DE3405487A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2522333B2 (ja) * 1987-08-31 1996-08-07 東洋製罐株式会社 表面に印刷された金属容器および金属容器の印刷方法
DE4110808A1 (de) * 1991-04-04 1992-10-08 Basf Ag Indolizintrimethinfarbstoffe
JP4938549B2 (ja) * 2007-05-15 2012-05-23 株式会社クボタ 作業車のグリル取り付け構造

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE704141C (de) * 1938-03-08 1941-03-24 I G Farbenindustrie Akt Ges Verfahren zur Sensibilisierung von Halogensilberemulsionen
US2503776A (en) * 1947-03-21 1950-04-11 Eastman Kodak Co Cyanine dyes containing a sulfohydrocarbon radical
US3052540A (en) * 1954-06-02 1962-09-04 Rca Corp Dye sensitization of electrophotographic materials
GB1020504A (en) * 1960-12-29 1966-02-16 Gevaert Photo Prod Nv Photoconductive recording materials
US3241959A (en) * 1963-07-29 1966-03-22 Eastman Kodak Co Sensitized electrophotographic composition
US3622316A (en) * 1964-10-05 1971-11-23 Polaroid Corp Photoresponsive articles comprising multilayer spectral sensitization systems
NL6713495A (fr) * 1966-10-07 1968-04-08
BE786207A (fr) * 1971-07-20 1973-01-15 Agfa Gevaert Nv Elektrofotografisch registreermateriaal
US3852067A (en) * 1971-11-04 1974-12-03 Polaroid Corp Photosensitive element with silver halide, a semiconductor and a sensitizing dye
JPS5722094B2 (fr) * 1974-12-24 1982-05-11
AU507694B2 (en) * 1975-06-14 1980-02-21 Hoechst Aktiengesellschaft Electrophotographic reproduction
JPS5772150A (en) * 1980-10-23 1982-05-06 Ishihara Sangyo Kaisha Ltd Electrophotographic sensitive material
DE3319654A1 (de) * 1983-05-31 1984-12-06 Hoechst Ag, 6230 Frankfurt Elektrophotographisches aufzeichnungsmaterial

Also Published As

Publication number Publication date
US4663261A (en) 1987-05-05
EP0152086A1 (fr) 1985-08-21
DE3405487A1 (de) 1985-08-22
JPS60192956A (ja) 1985-10-01
DE3560969D1 (en) 1987-12-17

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